Wool azo dyestuffs and process of making same



Patented May 3, 1932 UNITED STATES PATENT OFFIC GEORG KALISCHER AND RUDOLF SGHUELE, OF FRANKFORT-ON-THE-MAIN, AND HANS SGHINDHELM, 0F FRANKFORT-ON-THE-MAIN-FECHENHEIM, GERMANY, ASSIGINORS T0 GENERAL ANILINE WORKS, INC., OF NEW YORK, N. Y., A CORPORATION OF DELAWARE WOOL AZO DYESTUFFS AND PROCESS OF MAKING SAME No Drawing. Application filed September 11, 1930, Serial No. 481,346, and in Germany September 1'7, 1929.

Our present invention relates to new acid wool dyestuffs and to a process of making same.

These dyestuffs correspond to the general formula (wherein X means CH or O(CH or Y means any combining component and the Zs means hydrogen atoms which may be partially replaced by and wherein all benzene nuclei may contain further substituents). They are obtained by tetrazotizing a diamine of the formula (wherein X has the aforesaid signification and accordingly the benzene nuclei may contain further substituents) and combining the tetrazo compounds thus formed with 2 molecular proportions of combining components, at least one of which is of the formula (wherein Z has the above signification).

The present dyestuffs are distinguished by valuable shades, a remarkable fasteness to light and other properties fulfilling high practical requirements. This fact is the more surprising since 2.8-dil1ydroXy-napthalene-6- sulfonic acid used as combining component was hitherto of no industrial importance for the production of fast acid wool dyestuffs.

The favorable action of 2.8-dihydroxynaphthalene-6-sulfonic acid appears already if one residue of this acid is present in the molecule of the dyestuffs which are prepared in this case with the formation of a corresponding intermediate compound.

Those of the present dyestuffs which contain no aryl sulfo groups may be after treated with arylsulfochlorides and yield thereby esterified dyestuffs.

These latter dyestuffs show a likely good fastness and in some cases clearer and more yellowish shades than the original dyestuffs.

The tetrazo compounds used for the production of these dyestuffs are that of 4.4:- diamino diphenyl methane, 4.4--diaminotriphenyl-methane, 4.4-diamino-diphenyl-dimethyl-methane or nuclear substitution products of these compounds.

In order to further illustrate our invention the following examples are given, the parts being by weight and all temperatures in centigrade degrees, but we wish it to be understood that we are not limited to the particular products nor reaction conditions mentioned therein:

Example 1 22.6 parts of 4. L-diamino-diphenyl-dimethylmethane (obtained according to U. S. Patent No. 1,525,738) are dissolved in about 200 parts of water and 70 parts of hydrochlorio acid (specific gravity=1.15) and transformed into the tetrazo-compound in the customary manner by the addition of 13.8 parts of sodium nitrite, the temperature being maintained at nearly 0 by the addition of ice. The tetrazo solution is added to a solution of 52.4 parts of the sodium salt of 2.8-dihydroXy-naphthalene-6-sulfonic acid containing an amount of sodium carbonate or bicarbonate sufficient for maintaining a feebly alkaline reaction until the formation of the dyestuff has been finished. After some hours the dyestufi is isolated in the usual way by filtering and drying.

It corresponds to the probable formula It dyes wool red shades of very good fastness to washing and light.

The concentrated solution of this dyestuff is warmed with parato luene-sulfochloride with the addition of carbonate of so di um or of caustic soda solution.

The new esterified dyestutf thus obtained dyes very bright yellowish red shades of the same good fastness. also to milling, perspiration and sea-water.

A similar product is obtained by using as to run slowly while stirring into a solution of 51.? parts of the sodium salt of l-toluenesulfamino 8 hydroxy-napthalene-3.6-disulfonic, acid. Thereby an intermediate body is formed which may be precipitated by the addition of common salt. By adding it to a solution of 26.2 parts of the sodium salt of 2.8-dihydroXy-naphthalene-6-sulfonic acid a bright bluish claret red dyestufl' is obtained distinguished by a very good fastnessto washing. milling and light.

' The dyestufi thus produced corresponds to the probable formula H033 00Ha a Ha Ewample 3 19.8 parts of 4.4-diamino-diphenyl-methane are tetrazotized in the customary manner by means of 13 .8 parts of, nitrite at a tem-' perature not essentially exceeding 0. The tetrazo-compound is introduced while stirring into a solution maintained at 0, of 52.4 parts of the sodium salt of 2.8-dihydroxy-naphthalene-G-sulfonic acidand about, 45 parts of calcined soda. The formed dyestufi is isolated as usual by precipitating with common salt, filtering and drying. It dyes wool red shades of good fastness to washing and light. Itcorresponds to the formula By treating the concentrated hot solution of it'with para-toluene-sulfochloride and al-. kali, a dyestuflf of an essentially brighter shade and of the same fastn'ess is obtained.

Example, 4

When in Example 3 diamino-diphenyLmethane is replaced by 27.4: parts of 4. 1/-diamino-triphenylmethane and the process is otherwise carried out in the same way, a red dyestufi of a d f st es l cwashin nd. light is obtained. It corresponds to the. 01.- mula I i It may alsobe esterified inafhot alkaline. solution with para-toluene sulfochloride. Thereby a much brighter and more yellowishdyestuif of a very good fastness is obtained.

We claim:

1. Process which comprises'tetrazotizing a diamine of the general formula (wherein X means OI-I' or -C(CH3) or V H+ i v and all benzene nuclei may be substituted by alkyl or alkoxy groups), combining the tetrazo compound thus produced with 2 molecules of combining components, at least one of which is 2.8-dihydroxy-naphthalene*6- sulfonic acid of the formula and causing an arylsulfochloride of the benzene series to react on the alkaline solution of the formed dyestuffs.

2. Process which comprises tetrazotizing a diamine of the general formula combining the tetrazo compound thus produced with 2 molecules of 2.8-dihydroxynaphthalene-G-sulfonic acid of the formula and causing an aryl-sulfochloride of the benzene series to react on an alkaline solution of the formed dyestuffs.

3. Process which comprises tetrazotizing a diamine of the general formula diamine of the general formula combining the tetrazo compound thus pro duced with 2 molecules of 2.8-dihydroxynaphthalene-(isulfonic acid of the formula 5. As new compounds the acid wool dyestuffs of the general formula eces (wherein X means CH or C(CH or Y means any combining component and the Zs mean hydrogen atoms which may be partially replacedby HOsS (wherein X means CH or G(CH or and all benzene nuclei may be substituted by alkyl or alkoxy groups), combining the tetrazo compound thus produced with 2 molecules of combining components, at least one of which is 2.8clihydroXy-naphthalene-6- sulfonic acid of the formula 4. Process which comprises tetrazotizing a (wherein X means CH or C(CH or and the Zs mean hydrogen atoms which may be partially replaced by Os 0:- or oHPO's 03- and wherein all benzene nuclei may be substituted by alkyl or alkoxy groups) which compounds represent when dry colored powders dyeing wool from an acid bath reddish shades of a Very good fastness especially to light.

7. As new compounds the acid wooldyestuffs of the general formula be partially replaced by GEO-s02- B103 CH3 EH3 (wherein the Zs mean hydrogen atoms which are partially replaced by om-O-so which compounds represent when'dry colored powders dyeing Wool from an acid loath reddish shades of a very good fastness especially to light.

In testimony whereof, we'afiix our signatures. V

GEORG KALISCHER. RUDOLF SCHUELE. HANS SCHINDHELM.

(Where-iii the Zs mean hydrogen atoms which 

